The modification of textiles to provide temperature regulating properties through the generalized use of phase change materials (PCMs) is known. The use of microencapsulated PCM (mPCM), their methods of manufacture and applications thereof have also been widely disclosed. For example, the following references all use microcapsules in their application:    1. U.S. Pat. No. 5,366,801—Fabric with Reversible Enhanced Thermal Properties    2. WO0212607—Thermal Control Nonwoven    3. U.S. Pat. No. 6,517,648—Process for Preparing a Non-Woven Fibrous Web    4. JP05-156570—Fibrous Structure having Heat Storage Ability and its Production    5. US20040029472—Method and compound fabric with latent heat effect    6. US20040026659—Composition for Fabricating Phase-Change Material Microcapsules and a Method for Fabricating the Microcapsules    7. US20040044128—Method and Microcapsule Compound Waterborne Polyurethane    8. US2004011989—Fabric Coating Composition with Latent Heat Effect and Method for Fabricating the Same    9. US20020009473—Microcapsule, Method for its Production, Use of same, and Coating Liquid with Such    10. JP11350240—Production of Fiber having Adhered Microcapsule on Surface    11. JP2003-268679—Yarn having Heat Storage Property and Woven Fabric using the same.
Microcapsules, however, are expensive, can rupture, need additional resinous binders for adhesion, and can cause poor fabric flexibility and properties.
Numerous other disclosures outline the development of temperature regulating textiles by first manufacturing a fiber that contains a PCM or mPCM. For example, the following all disclose compositions, methods of manufacture, processes, and fabrics created from synthetically manufactured fibers. While this might be acceptable in some circumstances, the applications disclosed below omit all of the natural cellulosic and proteinaceous fibers and fabrics such as cotton, flax, leather, wool, silk, and fur. They also do not allow for the post treatment of synthetic fibers or fabrics.    12. US20030035951—Multi-Component Fibers having Enhanced Reversible Thermal Properties and Methods of Manufacturing Thereof.    13. U.S. Pat. No. 4,756,958—Fiber with Reversible Enhance Thermal Storage Properties and Fabrics made there from.    14. JP5331754—Heat Absorbing and Releasing Nonwoven Fabric of Conjugate Fiber    15. JP6041818—Endothermic and Exothermic Conjugate Fiber    16. JP5239716—Thermally Insulating Conjugate Fiber    17. JP8311716—Endothermic and Exothermic Conjugate Fiber    18. JP5005215—Endothermic and Exothermic Conjugate Fiber    19. JP2003027337—Conjugate Fiber Having Heat-Storing and Heat-Retaining Property    20. JP07-053917—Heat-Accumulating and Heat-Insulating Fiber    21. JP2003-293223—Endothermic Conjugate Fiber    22. JP02289916—Thermal Storage Fiber    23. JP03326189—Fiber with Heat Storage Ability    24. JP04-219349—Heat Storage Composition    25. JP06-234840—Heat Storage Material    26. JP Appl. #2001-126109—Heat Storage Fiber, Method of Producing the same, and Heat Storage Cloth Material    27. JP03352078—Heat Storage Material    28. JP04-048005—Fabric Product with Heat Storing Ability    29. WO0125511—Thermal Energy Storage Materials    30. JP02317329—Heat Storage Fiber-Method for Producing the same and Heat Storage Cloth Material    31. WO2004007631—Heat-Storage Material, Composition Therefore, and uses of these    32. JP2003-268358—Heat-Storage Material use around Body    33. JP2004-011032—Temperature-Controllable Fiber and Fabric    34. JP2004-003087—Heat Storable Composite Fiber and Cloth Material having Heat-Storing Properties    35. JP06200417—Conjugate Fiber Containing Heat-Accumulation Material and its Production    36. CN1317602—Automatic Temp-Regulating Fibre and its Products    37. U.S. Pat. No. 5,885,475—Phase Change Materials Incorporated throughout the Structure of Polymer Fibers
In addition, U.S. Pat. Nos. 4,851,291, 4,871,615, 4,908,238, and 5,897,952 disclose the addition of polyethylene glycol (PEG), polyhydric alcohol crystals, or hydrated salt PCM to hollow and non-hollow fibers. The fibers can be natural or synthetic, cellulosic, protein based, or synthetic hydrocarbon based. The non-hollow fibers have PEG materials deposited or reacted on the surface to act like PCM. These are problematic in that they are very hydrophilic causing excessive moisture absorption problems, and wash durability problems. There is no known disclosure of the use of acrylic, methacrylic polymers or other hydrophobic polymeric PCMs for these applications.
U.S. Pat. No. 6,004,662 mentions the use of acrylate and methacrylate polymers with C16 to C18 alkyl side chains as PCMs but not as unencapsulated or functionalized or reacted to the surface of fibrous textiles.
U.S. Pat. Nos. 4,259,198 and 4,181,643 disclose the use of crystalline crosslinked synthetic resin selected from the group of epoxide resins, polyurethane resins, polyester resins and mixtures thereof which contain, as crystallite forming blocks, segments of long-chain dicarboxylic acids or diols as PCMs, but not in conjunction with fibers or textiles.
Specific fiber and textile treatments or finishes in which specific compounds are reacted onto the substrate to provide some thermal change (usually based on moisture) have been disclosed. These systems are not based on long side chain alkyl, or long chain glycol acrylates or methacrylates that undergo a thermal phase change to provide improved latent heat effects. Examples include:    38. JP2003-020568—Endothermic Treating Agent for Fiber Material    39. JP2002-348780—Hygroscopic and Exothermic Cellulose-Based Fiber    40. JP2001-172866—Hygroscopic and Exothermic Cellulose-Based Fiber Product having Excellent Heat Retaining Property    41. JP11-247069—Warm Retainable Exothermic Cloth
Various disclosures describe the use of acrylic or methacrylic copolymers containing long chain alkyl moieties for textile finishes but only for properties such as grease repellency, soil resistance, permanent press properties, and quickness of drying. They do not disclose or mention the use of high purity polymers as PCMs, latent heat storage treatments or textile finishes which can impart temperature regulation and improved comfort. More specifically, they do not disclose advantageous polymer architecture such as mol. wt., mol. wt. distribution or specific copolymer architecture. Example include:    42. U.S. Pat. No. 6,679,924—Dye fixatives    43. U.S. Pat. No. 6,617,268—Method for protecting cotton from enzymatic attack by cellulase enzymes    44. U.S. Pat. No. 6,617,267—Modified textile and other materials and methods for their preparation    45. U.S. Pat. No. 6,607,994—Nanoparticle-based permanent treatments for textiles    46. U.S. Pat. No. 6,607,564—Modified textiles and other materials and methods for their preparation    47. U.S. Pat. No. 6,599,327—Modified textiles and other materials and methods for their preparation    48. U.S. Pat. No. 6,544,594—Water-repellent and soil-resistant finish for textiles    49. U.S. Pat. No. 6,517,933—Hybrid polymer materials    50. U.S. Pat. No. 6,497,733—Dye fixatives    51. U.S. Pat. No. 6,497,732—Fiber-reactive polymeric dyes    52. U.S. Pat. No. 6,485,530—Modified textile and other materials and methods for their preparation    53. U.S. Pat. No. 6,472,476—Oil- and water-repellent finishes for textiles    54. U.S. Pat. No. 6,387,492—Hollow polymeric fibers    55. U.S. Pat. No. 6,380,336—Copolymers and oil- and water-repellent compositions containing them    56. U.S. Pat. No. 6,379,753—Modified textile and other materials and methods for their preparation    57. US20040058006—High affinity nanoparticles    58. US20040055093—Composite fibrous substrates having protein sheaths    59. US20040048541—Composite fibrous substrates having carbohydrate sheaths    60. US20030145397—Dye fixatives    61. US20030104134—Water-repellent and soil-resistant finish for textiles    62. US20030101522—Water-repellent and soil-resistant finish for textiles    63. US20030101518—Hydrophilic finish for fibrous substrates    64. US20030079302—Fiber-reactive polymeric dyes    65. US20030051295—Modified textiles and other materials and methods for their preparation    66. US20030013369—Nanoparticle-based permanent treatments for textiles    67. US20030008078—Oil- and water-repellent finishes for textiles    68. US20020190408—Morphology trapping and materials suitable for use therewith    69. US20020189024—Modified textiles and other materials and methods for their preparation    70. US20020160675—Durable finishes for textiles    71. US20020155771—Modified textile and other materials and methods for their preparation    72. US20020152560—Modified textiles and other materials and methods for their preparation    73. US20020122890—Water-repellent and soil-resistant finish for textiles    74. US20020120988—Abrasion- and wrinkle-resistant finish for textiles
Although present compositions and methods are functional, they do not take advantage of the unique nature and functional aspects that accompanies the use of polymeric materials for the phase change material.
Polymers made with short chain, low molecular weight alkenes (olefins) are well known and used extensively. For example, polyethylene and polypropylene made from alkene monomers such as ethylene and propylene are well known as are copolymers of these monomers along with other alkene and other unsaturated monomers. In addition, one or more variations of the following polymers are known: Products from Dow Chemical Company such as the Affinity® and Engage® polymers (ethylene-octene copolymers); Versify® copolymers based on Ethylene-Propylene; Vistamaxx® products based on Ethylene-Propylene along with their Exact® copolymers based on Ethylene-Octene; other ethylene copolymers such as the Elvax® products based ethylene-vinyl acetate; Elvaloy® AC based on ethylene copolymerized with methyl, ethyl or butyl acrylate; and Nucrel® resins which are ethylene-methacrylic acid copolymers. These are all well-known commercial polymers in which the monomers have a random distribution in the chain.
Also available are other monomers with unsaturation that can be copolymerized with ethylene, for example, alkene monomers such as propene, butene, pentene, hexene, octene, decene, dodecene, isoprene, butadiene, or any other alkene functional compound and its isomers, alkenes with single or multiple unsaturations and their isomers, halogenated alkenes, reactive functional group alkenes with reactive functionality such as acids, alcohols, esters, ketones, aldehydes, ethers, epoxides, amides, and the other functionalities described below, cyclic alkenes with single or multiple unsaturations and their isomers, acrylic or methacrylic monomers and their isomers, non-functional, functional and reactive functional monomers, vinyl monomers such as vinyl ethers, vinyl esters, vinyl amides, halogenated vinyls, styrene, maleic anhydride, maleic acid, itaconic acid, itaconic anhydride, etc. and their isomers. These polymers and copolymers can be polymerized by a number of methods using such catalysts as Zeigler-Natta, free radical, and metallocene catalysts/initiators.
These catalysts do produce polymers and the catalysts themselves may be tailored to control the molecular weight of the polymer, the amount of branching in the polymer, the length of the branches in the polymer, the incorporation of comonomers and functional comonomers, the stereochemistry and chirality (atactic, isotactic or syndiotactic) of the polymer branches and its pendant groups, and the functionalization of the polymer chain ends.
U.S. Pat. Nos. 5,969,070, 6,566,544, 6,787,624, 7,119,154, 7,268,243, 7,300,994, 7,560,523, and 7,790,810, and US Patent Application Nos. 20070049714, 20080214854, 20090192278, 20100036077 and 20100029882 disclose various catalysts, polymers and stereochemistry of the polymers. However, none of this art discloses the aspects relating to precisely branched polymers disclosed herein, and particularly when used in conjunction with the temperature regulating material aspects that are disclosed herein.